SCHEDULED MAINTENANCE
Technetium(V) and rhenium(V) nitrido complexes
with bis(diphenyl-thiophosphoryl)amide,
N(SPPh2)2-
Abstract
Technetium(V) and rhenium(V) nitrido complexes
of the compositions [MNL
2
] and [MN(Cl)(PPhMe
2
)L]
have been synthesized by reaction of Na[N(SPPh
2
)
2
]
and [MNCl
2
(PPh
3
)
2
] or
[MNCl
2
(PPhMe
2
)
3
] complexes,
respectively [M = Re or Tc;
L = N(SPPh
2
)
2
-
].
The amide anion acts in all isolated complexes as a chelating ligand
co-ordinated via the sulfur atoms. The complexes
[TcN{N(SPPh
2
)
2
}
2
],
[ReN{N(SPPh
2
)
2
}
2
] and
[TcN(Cl)(PPhMe
2
)
2
{N(SPPh
2
)
2
}] have been studied by X-ray crystallography. The
bis-chelates are five-co-ordinate with the nitrogen atoms at the apexes
of square pyramids. The Tc atom in
[TcN(Cl)(PPhMe
2
)
2
{N(SPPh
2
)
2
}] has a distorted-octahedral co-ordination sphere with Cl
bonded trans to the nitrido function. The complex
[ReN{N(SPPh
2
)
2
}
2
] is the
first five-co-cordinate nitride which reacts with BCl
3
to
form a nitrido bridge between rhenium and boron;
[Re(NBCl
3
){N(SPPh
2
)
2
}
2
] is characterized by a covalent N–B bond of 1.539(5)
Å. The Re–N multiple bond distance is only slightly
influenced by addition of the Lewis acid. The complex
[ReN(Cl)(PPhMe
2
)
2
{N(SPPh
2
)
2
}] reacts with BCl
3
with substitution of
N(SPPh
2
)
2
-
and formation of the
well known
[Re(NBCl
3
)Cl
2
(PPhMe
2
)
3
]. The
corresponding technetium complexes do not form Tc–N–B
bridges upon reactions with BCl
3
. The
[MN(Cl)(PPhMe
2
)
2
{N(SPPh
2
)
2
}] (M = Tc or Re) complexes reacted with
S
2
Cl
2
to give thionitrosyl compounds with the
metals in lower oxidation states;
[Re(NS)Cl
2
(PPhMe
2
)
3
] and
[Re(NS)Cl
3
(PPhMe
2
)
2
] have been
characterized spectroscopically,
[Tc(NS)Cl
3
(PPhMe
2
)
2
] was studied by
X-ray diffraction and EPR spectroscopy. The phosphine ligands are
trans to each other.
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